Effect of NO₂ on nocturnal chemistry of isoprene: Gaseous oxygenated products and secondary organic aerosol formation

As one of the most abundant non-methane hydrocarbon in the atmosphere, isoprene has attracted lots of attention on its oxidation processes and environmental effects. However, less is known about the nocturnal chemistry of isoprene with multiple oxidants coexisting in the atmosphere. Besides, though highly oxygenated molecules (HOMs) have recently been recognized to contribute to secondary organic aerosol (SOA) formation, the specific contribution of measured HOMs on SOA formation in isoprene oxidation has not been well established. In this study, the oxidation of isoprene was simulated under dark and various NO₂/O₃ conditions. Plenty of oxidation products were identified by combining two state-of-the-art time-of-flight mass spectrometers, and more species with high C and N numbers and low volatilities were detected under high NO₂ conditions. The nocturnal oxidation of isoprene was found to be governed by synergic effects of multiple oxidants, including O₃, NO₃•, and •OH at the same time, and the oxidation proportions changed with NO₂. NO₂ promoted the formation of most N-containing products especially N2 products, because of the decisive role of NO₃• on their formation. Nevertheless, some products such as C₅H₁₀O_3–5, C₅H₁₁NO₆, and C₁₀H₁₆N₂O_10,11 showed a better correlation with HO₂NO₂ rather than NO₂/O₃, indicating the importance of HO₂• chemistry on the oxidation products formation. Though the concentration of measured oxygenated products was dominated by volatile and semi-volatile organic compounds, the low- and extremely low-volatile organic compounds contributed over 97 % to the SOA formation potential. However, challenges still exist in accurately simulating SOA formation from the measured oxygenated molecules to match the measurement, and further comprehensive characterization of oxidation products in both gas and aerosol phases at the molecular level is needed.